CN106443841B - A kind of ultralow residual reflectance ZnS substrates long wave antireflection film - Google Patents
A kind of ultralow residual reflectance ZnS substrates long wave antireflection film Download PDFInfo
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- CN106443841B CN106443841B CN201611000421.XA CN201611000421A CN106443841B CN 106443841 B CN106443841 B CN 106443841B CN 201611000421 A CN201611000421 A CN 201611000421A CN 106443841 B CN106443841 B CN 106443841B
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
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Abstract
The invention discloses a kind of ultralow residual reflectance ZnS substrates long wave antireflection films, are mainly characterized by：By using three kinds of germanium, zinc sulphide and yttrium fluoride thin-film material combinations, by the total physical thickness control of film layer in 2um or so；Two layers totally of heavily stressed yttrium fluoride film layer, maximum layer thickness are less than 0.4um.By be coated with the antireflection film can by zinc sulfide-based bottom in 7.5-9.7um wavelength bands maximum residual reflectivity is down to 0.5% hereinafter, average reflectance is down to 0.1% or less.The film layer is suitable for the surface antireflective processing at various zinc sulfide-based bottoms, can be prepared with the depositional mode of various thermal evaporations.
Description
Technical field
The invention belongs to optical film technology fields to be related to more particularly to optical element surface antireflection film technology
A kind of ultralow residual reflectance ZnS substrates long wave antireflection film.
Background technology
Zinc sulphide materials have good light transmission features in two wave bands of 3-5um and 8-12um, especially in 8-12um models
In enclosing compared with other infrared optical materials in addition to diamond, there is high mechanical strength, hardness height, thermal refractive index coefficient
Low, anti-rain corrodes the advantages that strong, is the head of the optical window of the infrared imagings such as current guided missile, bird and detection optical system
One of material selection.Since the refractive index of zinc sulphide materials is higher (~2.2), single side residual reflectance reaches~14%, uses width
Method with optics antireflection film can solve the problems, such as vulcanization zinc surface antireflective, to reduce the higher reflection loss in surface.
Currently, the thin-film material for being usually used in infrared band main Ge, Si, ZnS, ZnSe, MgF2、YF3、YbF3Deng part oxygen
Compound film (Al2O3、Y2O3、TiO2、HfO2Deng) infrared band can also be applied to.Since zinc sulphide window is generally operational in width
Spectral coverage (such as 7.5-9.7 μm, 8-12 μm, 7.5-11.5 μm), the antireflective of single thin film cannot meet the needs of bandwidth also not
Meets the needs of ultralow residual reflection, therefore wide band antireflective film must use the thin-film material alternating deposit of different refractivity
It forms, putting in order for film layer can be determined with thickness size by film design method.The design of multilayer wide band antireflective film
Method can be divided mainly into three classes：Regular design, non-regular design and unequal model design.1) regular design mainly passes through fixed film
The thickness gauge calculating of layer meets the matched thin-film refractive index of antireflective, selects thin-film material, nature to be not present according to refractive index
Refraction materials again use symmetric membrane to design replace.This method can not meet bandwidth and ultralow residual reflectance simultaneously
Demand.2) non-regular design is then optimized using multilayer film, based on numerical optimization according to residual reflectance
The physical thickness of objective optimization multilayer film, the method are generally used for the design of wide band antireflective film；3) design of unequal model
It is then the method using refractive index consecutive variations, realizes the transition from substrate refractive index to air refraction, but this method
There is high requirement to technology of preparing, it is still immature at present.The vulcanization zinc surface average residual reflectance value reported at present is general
0.5%, wide band antireflective film of the residual reflectance less than 0.2% has not been reported.
Invention content
(1) technical problems to be solved
The technical problem to be solved by the present invention is to：It is asked for 7.5-9.7um wavelength band zinc sulfide-based bottom surface antireflectives
Topic provides a kind of ultralow residual reflectance ZnS substrates long wave antireflection film, realizes that average residual reflectivity is low in broadband range
In 0.1% Film Design, the film structure designed has the characteristics that stress is small, stability is high, has in actually preparing
Stronger realizability.
(2) technical solution
In order to solve the above technical problem, the present invention provides a kind of ultralow residual reflectance ZnS substrates long wave antireflective is thin
Film, the antireflection film structure are：
Sub/x1H x2Lx3H x4M x5L x6M/Air
Wherein, substrate Sub is ZnS, and H, M and L respectively represent high refractive index, middle refractive index and low-index material, x1~x6
The optical thickness coefficient of every tunic is respectively represented, unit optical thickness is λ0/4。
Wherein, the high refractive index, middle refractive index and low-index material are respectively germanium, zinc sulphide and yttrium fluoride.
Wherein, the optical thickness coefficient per tunic is：x1=0.5298 ± 0.0265, x2=0.1411 ± 0.0071,
x3=1.0932 ± 0.0547, x4=0.5478 ± 0.0274, x5=0.2883 ± 0.0144, x6=0.3019 ± 0.0151.
The present invention also provides a kind of construction methods of antireflection film comprising following steps：
S1：Two layers of antireflective coating is built with female membrane system of wide band antireflective film；
S2：Film layer is replaced；
S3：The coefficient of every tunic is tentatively optimized based on numerical optimisation algorithms, obtains the optical thickness system of every tunic
Number.
Wherein, in the step S1, constructed basic film structure is as follows：
S/2H’L’/Air
Wherein, unit optical thickness is λ0/ 4, H ' and L ' respectively represent the unknown high and low refractive index material of refractive index, S generations
Table zinc sulfide-based bottom material, reference wavelength λ0。
Wherein, in the step S2, the high, medium and low thin-film material of selective refraction rate is respectively germanium, zinc sulphide and fluorination
Yttrium is respectively represented with H, M and L and is used with HLH combination replacement H ' materials for high refractive index, middle refractive index and low-index material
L ' materials are replaced in MLM combinations, and six layers of film structure is as follows：
Sub/x1H x2Lx3H x4M x5L x6M/Air
x1~x6The optical thickness coefficient of every tunic is respectively represented, unit optical thickness is λ0/4。
Wherein, in the step S3, calculating is optimized to thicknesses of layers using low residual reflectance as target, obtains x1~
x6Initial value：
Respectively：x1=0.5178 ± 0.0259, x2=0.1951 ± 0.0098, x3=0.8357 ± 0.0418, x4=
0.6313±0.0316,x5=0.3397 ± 0.0170, x6=0.2686 ± 0.0134.
Wherein, in the step S4, the upper thickness limit of L layers of limitation is less than 0.4um, again with low residual reflectance
For target, numerical optimization calculating is carried out, final x can be obtained1~x6Numerical value, respectively：x1=0.5298 ± 0.0265, x2
=0.1411 ± 0.0071, x3=1.0932 ± 0.0547, x4=0.5478 ± 0.0274, x5=0.2883 ± 0.0144, x6=
0.3019±0.0151。
(3) advantageous effect
The ultralow residual reflectance ZnS substrates long wave antireflection film that above-mentioned technical proposal is provided only used primary
Film to replacing, can effective ultralow residual reflectance of the optimization in 7.5-9.7 μ ms film layer structure, while by height
The material of stress carries out thickness control, avoids the risk that film layer falls off and cracks.Maximum residual reflection may be implemented in the present invention
0.5% or less rate, the 0.1% ultralow residual reflectance antireflection film of zinc sulfide-based bottom width band below of average residual reflectivity are set
Meter, membrane system have higher application value.
Description of the drawings
Fig. 1-vulcanization zinc surface wide band antireflective film schematic diagram.
Fig. 2-zinc sulphide materials optical constant.
Fig. 3-germanium material optical constant.
Fig. 4-yttrium fluoride materials optical constant.
Fig. 5-zinc sulphide materials single side residual reflectance.
Specific implementation mode
To keep the purpose of the present invention, content and advantage clearer, with reference to the accompanying drawings and examples, to the present invention's
Specific implementation mode is described in further detail.
The technical issues of in order to solve in the prior art, the present invention provide a kind of ultralow residual reflectance ZnS substrate long waves
Antireflection film, antireflection film structure are：
Sub/x1H x2Lx3H x4M x5L x6M/Air
Wherein, substrate Sub is ZnS, and H, M and L respectively represent high refractive index, middle refractive index and low-index material, x1~x6
The optical thickness coefficient of every tunic is respectively represented, unit optical thickness is λ0/4。
Further, high, medium and low refraction materials are respectively germanium, zinc sulphide and yttrium fluoride.
Often the optical thickness coefficient of tunic is：x1=0.5298 ± 0.0265, x2=0.1411 ± 0.0071, x3=
1.0932±0.0547,x4=0.5478 ± 0.0274, x5=0.2883 ± 0.0144, x6=0.3019 ± 0.0151.
Based on above-mentioned antireflection film structure, the construction method of the present embodiment antireflection film includes the following steps：
S1：Two layers of antireflective coating is built with female membrane system of wide band antireflective film.
Unit optical thickness is λ0/ 4, H ' and L ' respectively represent the unknown high and low refractive index material of refractive index, S represents sulphur
Change zinc-base bottom material, reference wavelength λ0, constructed basic film structure is as follows：
S/2H’L’/Air
S2：Film layer is replaced.
The high, medium and low thin-film material of selective refraction rate is respectively germanium, zinc sulphide and yttrium fluoride.It is respectively represented with H, M and L
It for high refractive index, middle refractive index and low-index material, is combined with HLH and replaces H ' materials, combined with MLM and replace L ' materials.
Film structure schematic diagram is as shown in Fig. 1, and six layers of film structure is as follows：
Sub/x1H x2Lx3H x4M x5L x6M/Air
x1~x6The optical thickness coefficient of every tunic is respectively represented, unit optical thickness is λ0/4。
S3：Coefficient based on six tunic of numerical optimisation algorithms pair is tentatively optimized, and x can be obtained1~x6Initial value.
Respectively：x1=0.5178 ± 0.0259, x2=0.1951 ± 0.0098, x3=0.8357 ± 0.0418, x4=
0.6313±0.0316,x5=0.3397 ± 0.0170, x6=0.2686 ± 0.0134.
Above step converts initial basic membrane system Shift Method using film, is target to film using low residual reflectance
Layer thickness optimizes calculating, effectively reduces the reflectivity at zinc sulfide-based bottom.
S4：The stress of low-index layer yttrium fluoride is larger, and film layer cracking or demoulding are susceptible to when its thickness is larger
The phenomenon that, it needs to control its thickness when building membrane system, the upper thickness limit of L layers of limitation is less than 0.4um.
Again using low residual reflectance as target, numerical optimization calculating is carried out, final x can be obtained1~x6Numerical value, point
It is not：x1=0.5298 ± 0.0265, x2=0.1411 ± 0.0071, x3=1.0932 ± 0.0547, x4=0.5478 ±
0.0274,x5=0.2883 ± 0.0144, x6=0.3019 ± 0.0151.
The step is under the premise of considering influence of the high stress film layer to membrane system stability, to the optimization meter of membrane system progress
It calculates.This step can not only ensure that film structure has ultralow residual reflectance, but also can effectively reduce answering for whole film layer
Power improves the stability and application reliability of film layer.
The method of the present invention is explained in further detail with specific example below.
(1) using zinc sulphide materials as substrate, it is mainly germanium, zinc sulphide and yttrium fluoride, design reference to select thin-film material
Wavelength X0It it is 8 μm, unit optical thickness is 2um.
Film structure is as shown in Fig. 1, and six layers of film structure is as follows：
Sub/x1H x2Lx3H x4M x5L x6M/Air
x1~x6Respectively represent the optical thickness coefficient of every tunic.
(2) optical constant of zinc sulphide materials is shown in attached drawing 2：The optical constant of germanium material is shown in attached drawing 3；The light of yttrium fluoride material
It learns constant and sees attached drawing 4.
(3) numerical optimisation algorithms are based on, using low residual reflectance as target, the optical thickness coefficient of six tunics is carried out just
Begin to optimize, obtains x1~x6Numerical value it is as follows：
x1=0.5178, x2=0.1951, x3=0.8357, x4=0.6313, x5=0.3397,
x6=0.2686.
(4) thickness limit of yttrium fluoride film again optimizes membrane system in 391nm, obtains x1~x6Final number
Value is as follows：
x1=0.5298, x2=0.1411, x3=1.0932, x4=0.5478, x5=0.2883,
x6=0.3019
The final membrane system of wide band antireflective film is as follows：
Sub|0.5298H 0.1411L 1.0932H 0.5478M 0.2883L 0.3019M|Air
At this point, being respectively by the first layer film to the corresponding physical thickness of outermost layer film of adjacent substrate：264.5nm,
191.6nm, 545.7nm, 492.9nm, 391.5nm and 271.6nm.Total physical thickness of the membrane system is in 2um or so.
Attached drawing 5 is shown in by the residual reflectance of upper wide band antireflective film obtained.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations
Also it should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of ultralow residual reflectance ZnS substrates long wave antireflection film, which is characterized in that the antireflection film structure
For：
Sub/x1H x2L x3H x4M x5L x6M/Air
Wherein, substrate Sub is ZnS, and H, M and L respectively represent high refractive index, middle refractive index and low-index material, x1~x6Respectively
The optical thickness coefficient per tunic is represented, unit optical thickness is λ0/ 4, λ0For reference wavelength, wave-length coverage 7.5-
9.7um。
2. ultralow residual reflectance ZnS substrates long wave antireflection film as described in claim 1, which is characterized in that the height
Refractive index, middle refractive index and low-index material are respectively germanium, zinc sulphide and yttrium fluoride.
3. ultralow residual reflectance ZnS substrates long wave antireflection film as claimed in claim 2, which is characterized in that described every
The optical thickness coefficient of tunic is：x1=0.5298 ± 0.0265, x2=0.1411 ± 0.0071, x3=1.0932 ± 0.0547,
x4=0.5478 ± 0.0274, x5=0.2883 ± 0.0144, x6=0.3019 ± 0.0151.
4. the construction method based on the antireflection film described in any one of claim 1-3, which is characterized in that including following step
Suddenly：
S1：Two layers of antireflective coating is built with female membrane system of wide band antireflective film；
S2：Film layer is replaced；
S3：The coefficient of every tunic is tentatively optimized based on numerical optimisation algorithms, obtains the optical thickness coefficient of every tunic；
S4：The stress of low-index layer yttrium fluoride is larger, is susceptible to when its thickness is larger film layer cracking or demoulding shows
As needing to control its thickness when building membrane system, the upper thickness limit of L layers of limitation is less than 0.4um；
Again using low residual reflectance as target, numerical optimization calculating is carried out, final x can be obtained1~x6Numerical value, respectively：
x1=0.5298 ± 0.0265, x2=0.1411 ± 0.0071, x3=1.0932 ± 0.0547, x4=0.5478 ± 0.0274, x5
=0.2883 ± 0.0144, x6=0.3019 ± 0.0151.
5. the construction method of antireflection film as claimed in claim 4, which is characterized in that constructed in the step S1
Basic film structure is as follows：
S/2H’L’/Air
Wherein, unit optical thickness is λ0/ 4, H ' and L ' respectively represent the unknown high and low refractive index material of refractive index, S represents sulphur
Change zinc-base bottom material, reference wavelength λ0, wave-length coverage 7.5-9.7um.
6. the construction method of antireflection film as claimed in claim 5, which is characterized in that in the step S2, selective refraction
The high, medium and low thin-film material of rate is respectively germanium, zinc sulphide and yttrium fluoride, is respectively represented as high refractive index, middle refraction with H, M and L
Rate and low-index material are combined with HLH and replace H ' materials, are combined with MLM and are replaced L ' materials, and six layers of film structure is as follows：
Sub/x1H x2L x3H x4M x5L x6M/Air
x1~x6The optical thickness coefficient of every tunic is respectively represented, unit optical thickness is λ0/4。
7. the construction method of antireflection film as claimed in claim 6, which is characterized in that in the step S3, with low residue
Reflectivity is that target optimizes calculating to thicknesses of layers, obtains x1~x6Initial value：
Respectively：x1=0.5178 ± 0.0259, x2=0.1951 ± 0.0098, x3=0.8357 ± 0.0418, x4=0.6313
±0.0316,x5=0.3397 ± 0.0170, x6=0.2686 ± 0.0134.
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| CN108196332B (en) * | 2017-11-20 | 2021-02-12 | 天津津航技术物理研究所 | Medium wave infrared reflection filtering film capable of filtering carbon dioxide infrared absorption interference |
| CN108227048B (en) * | 2018-01-26 | 2019-11-05 | 河南师范大学 | A kind of low-launch-rate infrared anti-reflection film on Silicon Wafer |
| CN108627889B (en) * | 2018-04-11 | 2021-01-15 | 上海欧菲尔光电技术有限公司 | Germanium substrate wide-spectrum infrared anti-reflection optical window |
| CN115079314B (en) * | 2022-07-25 | 2024-01-16 | 无锡泓瑞航天科技有限公司 | Mid-infrared spectrum optical window suitable for low-temperature and high-temperature environments |
| CN115980898B (en) * | 2023-03-21 | 2023-06-20 | 成都沃达惠康科技股份有限公司 | Multi-element multi-layer middle infrared high-reflection film and preparation method thereof |
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| JP5148839B2 (en) * | 2006-04-28 | 2013-02-20 | 株式会社堀場製作所 | Antireflection film for infrared light |
| CN101620280B (en) * | 2009-06-30 | 2011-01-26 | 中国航空工业集团公司洛阳电光设备研究所 | Film system of infrared double-waveband antireflection film system and plating method thereof |
| CN101738652B (en) * | 2009-12-15 | 2011-07-20 | 西南技术物理研究所 | Method for preparing ultrawide wave band high antireflection film combining three lights |
| JP2014032213A (en) * | 2010-11-30 | 2014-02-20 | Fujifilm Corp | Optical functional film for infrared rays |
| CN102338892B (en) * | 2011-09-29 | 2013-11-13 | 中国航空工业集团公司洛阳电光设备研究所 | Anti-reflection film with ZnS as substrate and large incidence angle at optical bands of 1064nm and 8-10mum and ZnS optical window |
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